Alkyl carbalkoxyalkyl and alkyl alkanoyloxyalkyl sulfites

ABSTRACT

NOVEL SULFITE ESTERS HAVING THE FORMULA   R-O-S(=O)-O-R&#39;&#39;   WHEREIN R IS AN ALKYL OR MONOHALOALKYL GROUP HAVING UP TO 12 CARBON ATOMS AND R&#39;&#39; IS A CARBALKOXY ALKYL OR ALKANOYLOXYALKYL GROUP OR A MONOHALOSUBSTITUTED DERIVATIVE THEREOF HAVING 3 TO 9 CARBON ATOMS, USEFUL AS HERBICIDES, INSECTICIDES AND NEMATOCIDES.

United States Patent 3,578,694 ALKYL CARBALKOXYALKYL AND ALKYLALKANOYLOXYALKYL SULFITES Rupert A. Covey, Wolcott, and Bogislav vonSchmeling and Charles E. Crittendon, Hamden, Conn., assignors toUniroyal, Inc., New York, N.Y. No Drawing. Filed Dec. 26, 1967, Ser. No.693,117 Int. Cl. A01n 9/14; C07c 137/00 US. Cl. 260-456 7 ClaimsABSTRACT OF THE DISCLOSURE Novel sulfite esters having the formula uROSOR',

wherein R is an alkyl or monohaloalkyl group having up to 12 carbonatoms and R is a carbalkoxy alkyl or alkanoyloxyalkyl group or amonohalosubstituted derivative thereof having 3 to 9 carbon atoms,useful as herbicides, insecticides and nematocides.

This invention relates to sulfite diesters having an alkyl or haloalkylgroup and a carbalkoxyalkyl or acyloxyalkyl group and their biologicaluses.

The compounds of the invention have the formula:

where R is an alkyl or monohaloalkyl group having from 1 to 18 carbonatoms, preferably 1 to 12 carbon atoms, and R is carbalkoxyalkyl oralkanoyloxyalkyl group having from 3 to 9 carbon atoms or theirmonohalosubstituted derivatives and the total carbon atom content ofsaid compound does not exceed 20.

Examples of R are methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec.-butyl, tert.-buty1, amyl, hexyl, 2-ethylhexyl, heptyl, octyl,nonyl, decyl, isodecyl, undecyl, dodecyl, hexadecyl, octadecyl, 2chloroethyl, 3 chlorobu l.

E xamples of R are carbomethoxymethyl, carbethoxymethyl,carbopropoxymethyl, carbobutoxymethyl, car bethoxyethyl,carbethoxybutyl, carbethoxychlorobutyl, 3- carbobutoxy 2 hexyl,acetoxyethyl, propionyloxyethyl, butyryloxyethyl, 2-acetoxypropyl,S-acetoxy 2 butyl, acetoxychlorobutyl.

The preparation of the chemicals of the invention may be carried out byreacting a hydroxyester with the separately prepared chlorosulfinate ofan alcohol, which may be made by reacting the alcohol with thionylchloride. Such preparation is illustrated by the following reactionswith the same symbols R, R as in the above general formula.

ll ROH SOC]: R-OSCI HOl i R-OSCI HOB. R-OSOR HCl The first reaction iscarried out at a temperature of between -5 C. and 30 C., preferablyabout 0 C., and the yield of chlorosulfinate is nearly quantitative. Aninert solvent such as benzene, xylene or solvent naphtha may be used,but is generally unnecessary. The second reaction is carried out in thepresence of an HCl acceptor, such as pyridine, dimethylaniline ortrimethyl- 3,578,694 Patented May 11, 1971 Preparation ofl-carbethoxyethyl octyl sulfite To 910 g. (7.0 moles) n-octyl alcoholcooled to 5- 10 was added dropwise with stirring 635 ml. (1040 g., 8.75moles) thionyl chloride keeping a maximum reaction temperature of 25.The mixture was allowed to stand 16 hours and then the dissolved HCl wasremoved with an aspirator. Further stripping of the chlorosulfinate wascarried out to 25 (3 mm.) by means of a vacuum pump. The yield is nearlyquantitative and the material is of sutlicient quality to be reacteddirectly in the next step.

To a cooled solution of 21.2 g. (0.1 mole) n-octyl chlorosulfinate in 25ml. benzene was added a solution of 13.0 g. (0.11 mole) ethyl lactateand 8.1 ml. (7.9 g., 0.1 mole) pyridine in 25 ml. benzene keeping thereaction temperature below 10". The mixture 'was stirred for 20 minutesand then was washed with 25 ml. water, 25 ml. 2 N NaOH and twice with 25ml. saturated salt solution. The organic layer was dried and the solventwas removed under reduced pressure. The product was distilled, B.P. -147(1.8 mm), yield 20.6 g. (70%).

Analysis.-Calcd. for C H O S (percent): S, 10.89. Found (percent): S,11.21.

An alternative method for preparing some of the compounds of theinvention involves reacting a chlorosulfinate with an epoxide. This is avery straightforward reaction giving nearly quantitative yields of pureproduct. However, in cases where the oxide is unsymmetrical, two isomersmay be obtained depending on how the oxide ring opens. This isillustrated by the following reaction:

CH JOOCZHE i t? 1 ROSOCHCHC1 ROSOCH-CHCI H COO 2H5 COOCzHa The followingexample illustrates the preparation of a sulfite by this method.

EXAMPLE II Preparation of 2-carbethoxy-2-chloro-l-methyl 2-chloroethylsulfite (and isomer) The preparation of 2-chloroethyl chlorosulfinate iswell known in the literature, e.g., US. 2,529,494 and 2,529,493.

To a solution of 16.3 g. (0.1 mole) 2-chloroethyl chlorosulfinate in 25m1. ether was added 13.7 g. (0.105 mole) ethyl 2,3-epoxybutyrate in 25ml. ether, while maintaining the reaction temperature at about 10. Themixture was stirred for 15 minutes and the ether and excessepoxybutyrate were removed under vacuum of 0.5 mm. Yield 29.2 g. (99%Analysis.-Calcd. for C H Cl O (percent): S, 10.93. Found (percent): S,10.99.

The last two compounds shown in Table I were prepared by this method.

Sulfur analyses of other chemicals of the present invention are shown inTable I.

TABLE I Sulfur analysis Calcd Found Carbethoxymethyl n-hexyl sulfite 12.70 12. 26 Carbethoxymethyl n-octyl sulfite. 12. 43 11. 99Carbethoxymethyl n-decyl sulfite. 10. 52 10. Carbethoxymethyl2ethylhexyl sulfito 11. 43 11. 20 Garbethoxymethyl tridecyl saint 9. 159. 08 Carbomethoxymethyl n-octyl sulfite. 12. 05 11. 89 Learbethoxyethylnoctyl sulfite 10. 89 11. 21 Lcarbobutoxyethyl n-decyl sulfite 9. l2 9.38 l-earbobutoxyethyl trideeyl sulfite. 8.14 8. 28 zacetoxyethyl n-deeylsulfite. 10.39 10.08 2 acetoxyethyl tridecyl sulfite 0. l5 9. l82-acetoxyethyl nbctyl sulfite. 11. 43 11. 52 Z-acetoxyethyl 2-octylsulfite 11. 43 10. 71 l carbethoxy-Lchloro-Z-propyl n-hcxyl sulfite andisomer 10. 20 9. 46 2-chloro-l0-carbomethoxydecyl 2-chloroethyl sulfiteand isomer 8. 49 8. 49

In accordance with this invention it has been discovered that sulfitesderived from hydroxy esters have outstanding chemical activity withregard to killing meristematic buds.

They may be used for killing meristematic buds on ornamental andagricultural herbaceous, semi-woody and woody plants such asChrysanthemum, cotton, azalea, apple and tobacco. Meristematic budsinclude both terminal and axillary buds. The selective killing ofterminal buds is an application for which the chemicals of the inventionare particularly useful.

Additionally, the compounds of the invention are usefulas insecticidesand nematocides.

For the several biological uses, the compounds of the present inventionmay be applied to plants, which term includes various plant parts suchas seeds, flowers, fruits, vegetables, roots and foliage in variousmanners. Seeds may be trated directly with the chemical before planting,or seeds may be treated with the chemical by incorporating the chemicalin the soil before or after planting the seeds. The chemicals may beapplied to plants in an inert medium as a dust in admixture with apowdered solid carrier, such as the various mineral silicates, e.g.,mica, talc, pyrophyllite and clays or as an aqueous composition, Thechemicals may be applied in admixture with small amounts ofsurface-active wetting agents, which may be anionic, non-ionic, orcationic surface-active agents, generally as aqueous compositions. Thechemicals may be dissolved in organic solvents such as acetone, benzene,or kerosene, and the solutions of the chemicals emulsified in water withthe aid of surface-active agents. Such surface-active agents are wellknown and reference is made to US. Pat. No. 2,547,724, columns 3 and 4,for detailed examples of the same. The chemicals of the invention may beadmixed with powdered solid carriers, such as mineral silicates,together with a surface-active agent so that a wettable powder may beobtained which may be applied directly to plants, or which may be shakenup with water for application to the plants in that form.

The concentration of active chemical in the useful chemical pruningformulations may vary widely, e.g., from 1% to 95%. Generally, theactive chemical in dispersions which are applied from 0.05% to 6.0%. Theamount per acre of active chemical applied may vary from 0.5 pound to 50pounds depending on the plant being treated and other factors known tothose skilled in the art.

Where the compounds are used as insecticides the concentration of activeingredient in the formulation ranges from 1 to 95%. Generally thedispersion which is applied has from 0.001 to 85% active chemical. Theapplication rate is 0.1 to 25 lbs. per acre of active chemical.

For nematocide application, formulations generally contain 0.001 to 90%of active chemical and the dispersions which are applied have from 0.001to 4.0%. Here the application rate ranges from 0.1 to 25 lbs. /acre.

The following example illustrates the use of the compounds of theinvention for killing meristematic buds:

EXAMPLE III Rooted cuttings of Chrysantheum morifolium cv. ImprovedIndianapolis Yellow are planted in 12 oz. styrofoam pots in a sterilizedsolid mixture of one part soil, one part peat moss, and one parthorticultural perlite. At planting and weekly thereafter, the plants arefertilized with 25-5-30 analysis fertilizer at the rate of one ounce perthree gallons of water. For seven to ten days following planting, theplants are placed under a polyethylene tent and frequently syringed toprovide conditions of both high temperature and high relative humidity,respectively. The potted plants are maintained under long-day conditionsby the use of supplemental fluorescent light from five pm. to. nine pm.and from five am. to seven a.m. daily. Ten days to two weeks afterplanting the established plants are ready to treat.

Two and one-half grams of the selected compound and 0.23 gram ofisooctyl phenyl polyethoxy ethanol are combined to produce anemulsifiable concentrate, of which is the active ingredient. Enoughwater is added to the 2.83 grams of emulsifiable concentrate to bringthe total volume to ml. This results in a 25,000 ppm. solution.Dilutions to 10,000, 4000 and 2000 ppm. are prepared by diluting theappropriate amount of the 25,000 ppm. solution with water to whichisooctyl phenyl polyethoxy ethanol has been added at the rate of twodrops per 100 ml.

The aqueous formulations are applied as a foliar spray until the plantsare wet to run-off. The plants are allowed to dry and then placed in thegreenhouse at a temperature of 65 F. minimum night temperature.

Within 12 to 24 hours following the application of optimum dosages andformulations of said compounds, the shoot apex, embryonic leaves andembryonic axillary meristems (hereinafter collectively referred to asthe terminal meristem) turn black and are 'very flaccid. Within the nextfew days this same dead tissue turns grayish and a constriction appearson the stem at the proximal limit of the killed tissue. At optimumconcentrations the compounds are non-phytotoxic to matured axillarymeristems, leaves, and stem tissue. This process of killing the terminalmeristem with aqueous emulsions of the compounds of the mentioned typewill hereinafter be referred to as chemical pruning.

At concentrations less than optimum the terminal meristern is notcompletely killed and therefore maintains apical dominance over theaxillary meristems. At concentrations in excess of optimum both theterminal and axillary meristems may be killed without causing damage tofoliage and stem tissue.

With other compounds, concentrations in excess of optimum may kill theterminal meristem and be phytotoxic to mature leaves but may not killthe axillary meristems. Concentrations in excess of optimum of stillother compounds may lkill the terminal and axillary meristems and bephytotoxic to the mature leaves.

The following table shows the minimum concentration of the compoundsrequired to achieve chemical pruning activity.

TABLE II Minimum pruning Compound: dosage (p.p.m.) Carbethoxymethyloctyl sulfite 4,000 Carbethoxymethyl decyl sul-fite 18,000Carbethoxymethyl Z-ethylhexylsuliite 23,000 Carbomethoxymethyl octylsulfite 2,000 l-carbethoxyethyl octyl sulfite 4,000 2-acetoxyethyl octylsulfite 6,000 Z-acetoxyethyl 2-octyl sulfite 14,000l-carbethoxy-1-chloro-2-propyl hexylsuliite 8,000

The activity of the chemicals of the present invention as insecticidesis shown in the following example:

EXAMPLE IV In the mosquito larvae test, mg. of chemical is dissolved in1 ml. of acetone and diluted to 100 ml. with tap water to give a 1-00p.p.m. solution. Dilution to 10 p.p.m. is made with tap water. Twentyfive ml. aliquots of each dosage, replicated once, are placed in testtubes and ten 4th instar larvae of Aedes aegypti are added and the tubesare held at 70 F. in darkness for 72 hours. At the end of this periodthe live and dead are counted and percent control calculated.

In the mite contact test, 400 mg. of chemical is dissolved in 10 ml. ofacetone and two drops of Triton X-100 This is then diluted to 200 ml.with distilled water to give a concentration of 2000 p.p.m.Four-week-old cotton seedlings grown in 12 oz. styrofoam cups are usedas the host plants. A quarter sized circle of tanglefoot is placed onboth primary leaves of each cotton plant in order to confine the mitesto the upper leaf surface. Approximately 24 hours prior to spraying withsaid chemicals, about ten two-spotted spider mites, T etranychusurticae, are placed inside each circle. Plants are sprayed to run-offwith the 2000 p.p.m. solution, using a concentrate sprayer which ispositioned 6" to 12" from the plants. One plant (2 leaves) is used ineach pot for-one replicate. Two replicates are used for each chemicaltested. Initial counts of the mites present are made shortly afterspraying. The plants are held lfive days in the greenhouse, at whichtime a final count is made of the live adult mites remaining on theleaves. The percent control is calculated by using Abbotts formula:

Percent control Percent mites living (untreated) -percent mites living(treated) X 100 Percent mites living (untreated) Table III shows theactivity of the alkyl carbalkoxy- The nematocidal activity of thecompounds is shown in the following example:

EXAMPLE V Three hundred milligrams chemical is dissolved in 10 ml. ofacetone. Ninety milligrams (three drops from a standard medicinedropper) of this 3.0% solution is 1 Isooctyl phenyl polyethoxy ethanolsurface active wetting agents.

added to a BPI standard water glass containing 150 mg. of a 0.01%solution of Triton X-l00 (five drops) in distilled water. Thirtymilligrams (1 drop) of a nematode suspension containing 50-100 livePanagrellus redivivus nematodes is added to the Watch glass containingthe chemical preparation. The final concentration of chemical in the BPIwatch glass is 1.0% (10,000 p.p.m.). The test is conducted in duplicateusing a dilution series. An untreated check, i.e., two watch glassescontaining 0.01% Triton X- solution and nematodes but no chemical, isincluded in the test. The watch glasses are placed in 100 x 15 mm.inverted Petri plates and sealed with water to avoid evaporation. Thetest is kept in the laboratory at room temperature. The results aretaken by microscopic inspection of the nematodes in the watch glasses.They are recorded as percent nematode control by contact after 48 hours.

Table IV shows the nematocidal activity of several carbalkoxyalkyl andalkyl acyloxyalkyl sulfites:

Having thus described our invention, what we claim and desire to protectby Letters Patent is: 1. A compound having the formula:

wherein R is an alkyl or mono-haloalkyl group having up to 12 carbonatoms and R is a canbalkoxyalkyl or alkanoyloxyalkyl group or amono-halo substituted derivative thereof having from 3 to 9 carbonatoms, and the total carbon atom content of said compound does notexceed 20.

2. The compound of claim 1 wherein R is a carbethoxyethyl group.

3. The compound of claim 1 wherein R is an acetoxyethyl group.

4. The compound of claim 1: carbethoxymethyl octyl sulfite.

5. The compound of claim 1: carbomethyl octyl sulfite.

6. The compound of claim 1: carbethoxyethyl octyl sulfite.

7. The compound of claim 1: 2-acetoxyethyl octyl sulfite.

References Cited UNITED STATES PATENTS 2,819,211 1/ 1958 Mikeska et a1260456 3,179,684 4/1965 Covey et al 260456 3,272,854 9/1966 Covey et al260456 LEON ZITVER, Primary Examiner L. DE CRESCENTE, Assistant ExaminerUS. Cl. X.R. 71-103; 424303 @2 3 UNITED STATES PATENT OFFICE CERTIFICATEOF CORRECTION Patent No. 3,578,694 D illgy 11. 1911 Inventor(s) RUPERTA, covEg et all It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Col.6, line #8, "carbomethyl" should read --carbomethoxymethyl-- Signedand sealed this 21 st day of December 1 971 (SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer ActingCommissionerof Patents

